Foam compositions

ABSTRACT

Foam compositions are provided. The compositions are prepared from multi-functional acetoacetate esters and multi-functional amines or acrylates. The foam compositions can include one or more additives. The foam compositions can be used for home and commercial insulation, air sealing, sound proofing, structural improvement, and exterior roofing, among other applications. The foam compositions provide advantages of being isocyanate free and offer reduced exposure to isocyanate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/982,142, filed on Apr. 21, 2014, which is incorporated herein byreference in its entirety.

TECHNICAL FIELD

The present disclosure relates generally to polymeric foam compositions,methods of using the compositions, and processes for preparing thecompositions.

BACKGROUND

Most current spray foam insulation liquid compositions are based on twocomponents, a polyol component and an isocyanate component that areseparate until the time of application. The isocyanate is typicallycomposed of methylene diphenyl diisocyanate (MDI), which whenaerosolized exists as very fine airborne droplets. Exposure toaerosolized MDI can pose a severe health threat (e.g., allergicsensitization). Accordingly, there exists a need for spray foams thateliminate the use of MDI and provide systems safer to the applicator andto nearby personnel.

SUMMARY

In one aspect, disclosed is foam comprising the reaction product of acompound of formula (a) with a compound of formula (b); or the reactionproduct of a compound of formula (a) with a compound of formula (c);

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms; an aromatic group; a heteroaromatic group; anda heterocyclic group; or any combination thereof wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents; m is 2 to 200; and n is 2 to 200.

In another aspect, disclosed are methods of preparing the foamcompositions.

In another aspect, disclosed are methods of using the foam compositions.

DETAILED DESCRIPTION

Disclosed are rigid and semi-rigid foam compositions, methods of makingthe compositions, and methods of using the compositions. Thecompositions are particularly useful for insulation applications (e.g.,home and commercial use), air sealing, sound proofing, structuralimprovement, and exterior roofing, for example. The foam compositionscan be applied via a two-part system (a plural component spray system),where the reactants are mixed at a 0.5-1.0:0.5-1.0 by volume basis(e.g., 0.5:1, 1:1, or 1:0.5 by volume basis). The foam compositions canbe “open cell foams,” “closed cell foams,” or a combination thereof.

The disclosed foam compositions provide several advantages. As oneadvantage, the compositions contain no isocyanate containing compounds,and consequently, the hazards associated with aerosolized isocyanate areeliminated. As another advantage, the foam compositions can bebiocompatible. For example, the compositions can be derived frombiocompatible monosaccharides, disaccharides, oligosaccharides,polysaccharides, and glycerine materials. As another advantage, the foamcompositions may provide for in situ generation of blowing agent,eliminating the need for additional blowing agents to produce the foam.For example, the compositions can be derived from components that yieldwater upon reaction, and the water may act as a chemical blowing agent.Use of water as a blowing agent can provide rigid or semi-rigid foams.

In one aspect, the foams are provided by reaction of multi-functionalacetoacetate esters with multi-functional amines. The acetoacetateesters can be disposed upon any selected substrate (e.g., a hydrocarbonchain, a monosaccharide, a disaccharide, a backbone polymer). Themultifunctional amine can be, for example, an alkyldiamine, an aromaticdiamine, or an amine-functionalized polymer. Reaction of theacetoacetate ester with the amine results in formation of an iminefunction (or its enamine tautomer), thereby linking the monomer units.The multi-functionality of the monomers and reaction thereof providesfor a cross-linked polymeric structure, exemplified as a rigid orsemi-rigid foam.

In another aspect, the foams are provided by a Michael addition reactionbetween multi-functional acetoacetate esters and diacrylate compounds.Reaction of the multiple functionalities of the monomer startingmaterials provides for a cross-linked polymeric structure, exemplifiedas a rigid or semi-rigid foam.

1. DEFINITION OF TERMS

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “an” and “the” include plural references unless the context clearlydictates otherwise. The present disclosure also contemplates otherembodiments “comprising,” “consisting of” and “consisting essentiallyof,” the embodiments or elements presented herein, whether explicitlyset forth or not.

The conjunctive term “or” includes any and all combinations of one ormore listed elements associated by the conjunctive term. For example,the phrase “an apparatus comprising A or B” may refer to an apparatusincluding A where B is not present, an apparatus including B where A isnot present, or an apparatus where both A and B are present. The phrases“at least one of A, B, . . . and N” or “at least one of A, B, . . . N,or combinations thereof” are defined in the broadest sense to mean oneor more elements selected from the group comprising A, B, . . . and N,that is to say, any combination of one or more of the elements A, B, . .. or N including any one element alone or in combination with one ormore of the other elements which may also include, in combination,additional elements not listed.

The modifier “about” used in connection with a quantity is inclusive ofthe stated value and has the meaning dictated by the context (forexample, it includes at least the degree of error associated with themeasurement of the particular quantity). The modifier “about” shouldalso be considered as disclosing the range defined by the absolutevalues of the two endpoints. For example, the expression “from about 2to about 4” also discloses the range “from 2 to 4.” The term “about” mayrefer to plus or minus 10% of the indicated number. For example, “about10%” may indicate a range of 9% to 11%, and “about 1” may mean from0.9-1.1. Other meanings of “about” may be apparent from the context,such as rounding off, so, for example “about 1” may also mean from 0.5to 1.4.

As used herein, the term “suitable substituent” is intended to mean achemically acceptable functional group (i.e., a moiety that does notnegate the activity of the disclosed foam compositions). Illustrativeexamples of suitable substituents include, but are not limited to, halogroups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups,alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercaptogroups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups,aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups,aralkoxy or heteroaralkoxy groups, HO—(C═O)— groups, heterocylic groups,cycloalkyl groups, amino groups, alkyl- and dialkylamino groups,carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups,alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonylgroups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonylgroups and the like. Those skilled in the art will appreciate that manysubstituents can be substituted by additional substituents.

As used herein, the term “alkenyl” refers a straight or branchedhydrocarbon chain containing from 2 to 10 carbons and containing atleast one carbon-carbon double bond formed by the removal of twohydrogens. Representative examples of alkenyl include, but are notlimited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl,4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl, and 3-decenyl.Alkenyl groups may be unsubstituted or substituted by one or moresuitable substituents, preferably 1 to 3 suitable substituents, asdefined above.

As used herein, the term “alkoxy” refers to an alkyl group, as definedherein, appended to the parent molecular moiety through an oxygen atom.Representative examples of alkoxy include, but are not limited to,methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, andhexyloxy.

As used herein, the term “alkyl” refers to a linear or branchedhydrocarbon radical having the specified number of carbon atoms. Theterm “C₁-C₆-alkyl” is defined to include alkyl groups having 1, 2, 3, 4,5, or 6 carbons in a linear or branched arrangement. For example,“C₁-C₆-alkyl” specifically includes methyl, ethyl, n-propyl, i-propyl,n-butyl, t-butyl, i-butyl, pentyl, and hexyl. Alkyl groups may beunsubstituted or substituted by one or more suitable substituents,preferably 1 to 3 suitable substituents, as defined above.

As used herein, the term “alkynyl” refers to a straight or branchedhydrocarbon radical having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbons, andhaving one or more carbon-carbon triple bonds. Alkynyl groups include,but are not limited to, ethynyl, propynyl, and butynyl. Alkynyl groupsmay be unsubstituted or substituted by one or more suitablesubstituents, preferably 1 to 3 suitable substituents, as defined above.

As used herein, the term “amino” refers to an —NH₂ group.

As used herein, the term “aminoalkyl” refers to at least one aminogroup, as defined herein, appended to the parent molecular moietythrough an alkyl group, as defined herein. Representative examples ofaminoalkyl include, but are not limited to, aminomethyl, 2-aminoethyl,and 2-aminopropyl.

As used herein, the term “aryl” means monocyclic, bicyclic, or tricyclicaromatic radicals. Representative examples of the aryl groups include,but are not limited to, phenyl, dihydroindenyl, indenyl, naphthyl,dihydronaphthalenyl, and tetrahydronaphthalenyl. Aryl groups may beoptionally substituted by one or more suitable substituents, preferably1 to 5 suitable substituents, as defined above.

As used herein, the term “carbonyl” or “(C═O)” (as used in phrases suchas alkylcarbonyl, alkyl —(C═O)— or alkoxycarbonyl) refers to the joinderof the >C═O moiety to a second moiety such as an alkyl or amino group(i.e. an amido group).

Alkoxycarbonylamino (i.e. alkoxy(C═O)—NH—) refers to an alkyl carbamategroup. The carbonyl group is also equivalently defined herein as (C═O).Alkylcarbonylamino refers to groups such as acetamide.

As used herein, the term “cycloalkyl” refers to a mono, bicyclic ortricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl,bicyclo[3.2.1]octanyl and bicyclo[5.2.0]nonanyl, etc.); optionallycontaining 1 or 2 double bonds. Cycloalkyl groups may be unsubstitutedor substituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

As used herein, the term “halogen” or “halo” refers to a fluoro, chloro,bromo or iodo radical.

As used herein, the term “haloalkyl” refers to an alkyl group, asdefined herein, substituted by one, two, three, or four halogen atoms.Representative examples of haloalkyl include, but are not limited to,chloromethyl, 2-fluoroethyl, trifluoromethyl, pentafluoroethyl,2-chloro-3-fluoropentyl, and 4,4,4,-trifluorobutyl.

As used herein, the term “heteroaryl” refers to a monocyclic heteroarylor a bicyclic heteroaryl. The monocyclic heteroaryl is a five- orsix-membered ring. The five-membered ring contains two double bonds. Thefive-membered ring may contain one heteroatom selected from O or S; orone, two, three, or four nitrogen atoms and optionally one oxygen orsulfur atom. The six-membered ring contains three double bonds and one,two, three or four nitrogen atoms. Representative examples of monocyclicheteroaryl include, but are not limited to, furanyl, imidazolyl,isoxazolyl, isothiazolyl, oxadiazolyl, 1,3-oxazolyl, pyridinyl,pyridazinyl, pyrimidinyl, pyrazinyl, pyrazolyl, pyrrolyl, tetrazolyl,thiadiazolyl, 1,3-thiazolyl, thienyl, triazolyl, and triazinyl. Thebicyclic heteroaryl includes a monocyclic heteroaryl fused to a phenyl,or a monocyclic heteroaryl fused to a monocyclic cycloalkyl, or amonocyclic heteroaryl fused to a monocyclic cycloalkenyl, or amonocyclic heteroaryl fused to a monocyclic heteroaryl, or a monocyclicheteroaryl fused to a monocyclic heterocycle. Representative examples ofbicyclic heteroaryl groups include, but are not limited to,benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl,benzoxadiazolyl, 6,7-dihydro-1,3-benzothiazolyl,imidazo[1,2-a]pyridinyl, indazolyl, indolyl, isoindolyl, isoquinolinyl,naphthyridinyl, pyridoimidazolyl, quinazolinyl, quinolinyl,thiazolo[5,4-b]pyridin-2-yl, thiazolo[5,4-d]pyrimidin-2-yl, and5,6,7,8-tetrahydroquinolin-5-yl. Heteroaryl groups may be unsubstitutedor substituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

As used herein, the term “heterocycle” or “heterocyclyl” refers to amonocyclic heterocycle, a bicyclic heterocycle, or a tricyclicheterocycle. The monocyclic heterocycle is a three-, four-, five-, six-,seven-, or eight-membered ring containing at least one heteroatomindependently selected from the group consisting of oxygen, nitrogen,phosphorus and sulfur. The three- or four-membered ring contains zero orone double bond, and one heteroatom selected from the group consistingof oxygen, nitrogen, phosphorus and sulfur. The five-membered ringcontains zero or one double bond and one, two or three heteroatomsselected from the group consisting of oxygen, nitrogen, phosphorus andsulfur. The six-membered ring contains zero, one or two double bonds andone, two, or three heteroatoms selected from the group consisting ofoxygen, nitrogen, phosphorus and sulfur. The seven- and eight-memberedrings contains zero, one, two, or three double bonds and one, two, orthree heteroatoms selected from the group consisting of oxygen,nitrogen, phosphorus and sulfur. Representative examples of monocyclicheterocycles include, but are not limited to, azetidinyl, azepanyl,aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl,1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl,isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl,oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, phosphinane,piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl,pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl,tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothienyl,thiadiazolinyl, thiadiazolidinyl, thiazolinyl, thiazolidinyl,thiomorpholinyl, 1,1-dioxidothiomorpholinyl (thiomorpholine sulfone),thiopyranyl, and trithianyl. The bicyclic heterocycle is a monocyclicheterocycle fused to a phenyl group, or a monocyclic heterocycle fusedto a monocyclic cycloalkyl, or a monocyclic heterocycle fused to amonocyclic cycloalkenyl, or a monocyclic heterocycle fused to amonocyclic heterocycle, or a bridged monocyclic heterocycle ring systemin which two non-adjacent atoms of the ring are linked by an alkylenebridge of 1, 2, 3, or 4 carbon atoms, or an alkenylene bridge of two,three, or four carbon atoms. Representative examples of bicyclicheterocycles include, but are not limited to, benzopyranyl,benzothiopyranyl, chromanyl, 2,3-dihydrobenzofuranyl,2,3-dihydrobenzothienyl, azabicyclo[2.2.1]heptyl (including2-azabicyclo[2.2.1]hept-2-yl), 2,3-dihydro-1H-indolyl, isoindolinyl,octahydrocyclopenta[c]pyrrolyl, octahydropyrrolopyridinyl,9-phosphabicyclo[3.3.1]nonane, 8-phosphabicyclo[3.2.1]octane, andtetrahydroisoquinolinyl. Tricyclic heterocycles are exemplified by abicyclic heterocycle fused to a phenyl group, or a bicyclic heterocyclefused to a monocyclic cycloalkyl, or a bicyclic heterocycle fused to amonocyclic cycloalkenyl, or a bicyclic heterocycle fused to a monocyclicheterocycle, or a bicyclic heterocycle in which two non-adjacent atomsof the bicyclic ring are linked by an alkylene bridge of 1, 2, 3, or 4carbon atoms, or an alkenylene bridge of two, three, or four carbonatoms. Examples of tricyclic heterocycles include, but are not limitedto, octahydro-2,5-epoxypentalene,hexahydro-2H-2,5-methanocyclopenta[b]furan,hexahydro-1H-1,4-methanocyclopenta[c]furan, aza-admantane(1-azatricyclo[3.3.1.1^(3,7)]decane), oxa-adamantane(2-oxatricyclo[3.3.1.1^(3,7)]decane), and2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane. Heterocyclic groupsmay be unsubstituted or substituted by one or more suitablesubstituents, preferably 1 to 3 suitable substituents, as defined above.

As used herein, the term “hydroxy” refers to an —OH group.

As used herein, the term “hydroxyalkyl” refers to an alkyl group, asdefined herein, substituted by at least one hydroxy group.Representative examples of hydroxyalkyl include, but are not limited to,hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl,2,3-dihydroxypentyl, 4-hydroxybutyl, 2-ethyl-4-hydroxyheptyl,3,4-dihydroxybutyl, and 5-hydroxypentyl.

A prefix attached to a multi-component substituent only applies to thefirst component it precedes. To illustrate, the term “alkylcycloalkyl”contains two components: alkyl and cycloalkyl. Thus, the C₁-C₆-prefix onC₁-C₆-alkylcycloalkyl means that the alkyl component of thealkylcycloalkyl contains from 1 to 6 carbon atoms; the C₁-C₆-prefix doesnot describe the cycloalkyl component. To illustrate further, the prefix“halo” on haloalkoxyalkyl indicates that only the alkoxy component ofthe alkoxyalkyl substituent is substituted with one or more halogenradicals. If the halogen substitution may only occur on the alkylcomponent, the substituent would instead be described as“alkoxyhaloalkyl.”

A substituent is “substitutable” if it comprises at least one carbon ornitrogen atom that is bonded to one or more hydrogen atoms. Thus, forexample, hydrogen, halogen, and cyano do not fall within thisdefinition. In addition, a sulfur atom in a heterocyclyl containing suchatom is substitutable with one or two oxo substituents.

If a substituent is described as being “substituted”, a non-hydrogenradical is in the place of hydrogen radical on a carbon or nitrogen ofthe substituent. Thus, for example, a substituted alkyl substituent isan alkyl substituent in which at least one non-hydrogen radical is inthe place of a hydrogen radical on the alkyl substituent. To illustrate,monofluoroalkyl is alkyl substituted with a fluoro radical, anddifluoroalkyl is alkyl substituted with two fluoro radicals. It shouldbe recognized that if there is more than one substitution on asubstituent, each non-hydrogen radical may be identical or different(unless otherwise stated).

When a substituent is referred to as “unsubstituted” or not referred toas “substituted” or “optionally substituted”, it means that thesubstituent does not have any substituents. If a substituent isdescribed as being “optionally substituted”, the substituent may beeither (1) not substituted or (2) substituted. If a substituent isdescribed as being optionally substituted with up to a particular numberof non-hydrogen radicals, that substituent may be either (1) notsubstituted; or (2) substituted by up to that particular number ofnon-hydrogen radicals or by up to the maximum number of substitutablepositions on the substituent, whichever is less. Thus, for example, if asubstituent is described as a heteroaryl optionally substituted with upto 3 non-hydrogen radicals, then any heteroaryl with less than 3substitutable positions would be optionally substituted by up to only asmany non-hydrogen radicals as the heteroaryl has substitutablepositions. To illustrate, tetrazolyl (which has only one substitutableposition) would be optionally substituted with up to one non-hydrogenradical. To illustrate further, if an amino nitrogen is described asbeing optionally substituted with up to 2 non-hydrogen radicals, then aprimary amino nitrogen will be optionally substituted with up to 2non-hydrogen radicals, whereas a secondary amino nitrogen will beoptionally substituted with up to only 1 non-hydrogen radical.

If substituents are described as being “independently selected” from agroup, each substituent is selected independent of the other. Eachsubstituent, therefore, may be identical to or different from the othersubstituent(s).

As used herein, the term “open-cell” refers to individual cells that areruptured or open or interconnected producing a porous “sponge” foam,where the gas phase can move around from cell to cell.

As used herein, the term “closed-cell” refers to individual cells thatare discrete, such that each closed-cell is enclosed by polymericsidewalls that minimize the flow of a gas phase from cell to cell. Itshould be noted that the gas phase may be dissolved in the polymer phasebesides being trapped inside the closed-cell. Furthermore, the gascomposition of the closed-cell foam at the moment of manufacture doesnot necessarily correspond to the equilibrium gas composition afteraging or sustained use. Thus, the gas in a closed-cell foam frequentlyexhibits compositional changes as the foam ages.

2. FOAM COMPOSITIONS

In one aspect, disclosed are foam compositions having repeating units offormula (I),

wherein

each R^(x) represents a group of formula:

each R^(y) represents a group of formula:

A and B, at each occurrence, are each independently selected from asaturated or unsaturated, linear, branched, or cyclic hydrocarbon group,wherein each hydrocarbon group optionally includes one or moreheteroatoms (e.g., oxygen, nitrogen, sulfur, silicon, or phosphorous);an aromatic group; a heteroaromatic group; and a heterocyclic group; orany combination thereof; wherein said groups, at each occurrence, areindependently unsubstituted or substituted with one or more suitablesubstituents; and

s and t, at each occurrence, are each independently an integer selectedfrom 1 to 200, preferably 1 to 20.

It is to be understood that the imine functionality (also referred to asa Schiff base) in the repeating units of formula (I) may exist as itsenamine tautomer. For example, the repeating units of formula (I) mayalso be depicted as follows:

wherein R^(x), R^(y), A, B, s, and t are as defined above.

In certain embodiments, A is a C₁-C₂₀ hydrocarbon group. In certainembodiments, A is a saturated, linear or branched C₁-C₂₀ hydrocarbongroup. In certain embodiments, A is a linear C₆ hydrocarbon group. Incertain embodiments, A is a linear C₄ hydrocarbon group. In certainembodiments, A is a linear C₃ hydrocarbon group. In certain embodiments,A is a group of formula:

wherein s is 2 at each occurrence.

In certain embodiments, A is a heterocyclic group. In certainembodiments, A is a group of formula:

or any combination thereof

In certain embodiments, each A is independently selected from a linearC₃ hydrocarbon group, a linear C₄ hydrocarbon group, a linear C₆hydrocarbon group, and a heterocyclic group. In certain embodiments,each A is independently selected from a linear C₃ hydrocarbon group anda heterocyclic group. In certain embodiments, each A is a group offormula:

or any combination thereof

In certain embodiments, each A is derived from a multi-functionalacetoacetate ester compound. In certain embodiments, A is derived fromhydrocarbon compounds with two or more acetoacetate groups. Suitablemulti-functional acetoacetate ester compounds include, for example,alkyl diol diacetoacetates (also known as alkyl diol bisacetoacetates)such as, for example, butane diol diacetoacetate, 1,6-hexanedioldiacetoacetate, neopentylglycol diacetoacetate,4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane diacetoacetate,2-methyl-1,3-propanediol diacetoacetate, ethylene glycol diacetoacetate,propylene glycol diacetoacetate; cyclohexanedimethanol diacetoacetate;other diol diacetoacetates; alkyl triol triacetoacetates (also known asalkyl triol trisacetoacetates), such as, for example, trimethylolpropane triacetoacetate, pentaerythritol triacetoacetate, glyceroltriacetoacetate, or trimethylolethane triacetoacetate; and the like.Further examples of suitable multi-functional acetoacetate estercompounds include tetra-, penta-, and higher acetoacetates of polyhydricalcohols (i.e., polyhydric alcohols on which four, five, or morehydroxyl groups are linked to acetoacetate groups through esterlinkages), including, for example, pentaerythritol tetraacetoacetate,dipentaerythritol pentaacetoacetate, and dipentaerythritolhexaacetoacetate. Further examples of suitable multi-functionalacetoacetate ester compounds include ethylene glycol bisacetoacetate,1,2-propanediol bisacetoacetate, 1,3-propanediol bisacetoacetate,1,4-butanediol bisacetoacetate, neopentyl glycol bisacetoacetate,isosorbide bisacetoacetate, trimethylol propane tris acetoacetate,glycerol tris acetoacetate, castor oil tris acetoacetate, glucoseacetoacetates (e.g., glucose tris acetoacetate, and glucose tetraacetoacetate), sucrose acetoacetates, sorbitol acetoacetates (e.g.,sorbitol tris acetoacetate, and sorbitol tetra acetoacetate), anderythritol acetoacetates.

In certain embodiments, A is derived from a multi-functionalacetoacetate ester of a monosaccharide, a disaccharide, anoligosaccharide, a polysaccharide, or a combination thereof. In certainembodiments, A is derived from a multi-functional acetoacetate ester ofglucose, fructose, galactose, sucrose, lactulose, lactose, maltose,trehalose, celloboise, kojibiose, nigerose, isomaltose, β,β-trehalose,α,β-trehalose, sophorose, laminaribiose, gentiobiose, turanose,maltulose, palatinose, gentiobiulose, mannobiose, melibiose,melibiulose, rutinose, rutinulose, xylobiose, fructo-oligosaccharides,galactooligosaccharides, mannan oligosaccharides, arabinoxylans,cellulose, chitin, pectins, or a combination thereof. In certainembodiments, A is derived from a multi-functional acetoacetate ester ofsucrose. In certain embodiments, A is derived from a multi-functionalacetoacetate ester of sorbitol. In certain embodiments, A is derivedfrom a multi-functional acetoacetate ester of erythritol.

In certain embodiments, B is a C₁-C₂₀ hydrocarbon group. In certainembodiments, B is a saturated, linear or branched C₁-C₂₀ hydrocarbongroup. In certain embodiments, B is a saturated, linear or branchedC₂-C₁₀ hydrocarbon group. In certain embodiments, B is a group offormula:

wherein t is 1 at each occurrence.

In certain embodiments, B is arylalkyl, and more specifically, anaryl-dialkyl group. In certain embodiments, B is a group of formula:

wherein t is 1 at each occurrence.

In certain embodiments, B is a group of formula:

or any combination thereof

In certain embodiments, B is derived from a multi-functional aminecompound. In certain embodiments, B is derived from an alkylene diamine,an alkylene triamine, an alkylene tetraamine, or the like. In certainembodiments, B is derived from an aromatic-containing multi-functionalamine. Suitable multi-functional amine compounds include, for example,ethylene diamine, hexamethylene diamine, 2-methyl-1,5-diaminopentane,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,meta-phenylenediamine, para-phenylenediamine, meta-xylenediamine, anddiaminodiphenyl sulfone.

In certain embodiments, s, at each occurrence, is independently selectedfrom 2, 3, 4, 5, 6, 7, and 8. In certain embodiments, s is 2 at eachoccurrence. In certain embodiments, t, at each occurrence, isindependently selected from 1, 2, 3, 4, and 5. In certain embodiments, tis 1 at each occurrence.

In certain embodiments, the foam compositions have formula (I-a),

wherein A and B are as defined above.

In certain embodiments, the foam compositions have formula (I-b),

In another aspect, disclosed are foam compositions having repeatingunits of formula (II),

wherein

each R^(w) represents a group of formula:

each R^(z) represents a group of formula:

A and B, at each occurrence, are each independently selected from asaturated or unsaturated, linear, branched, or cyclic hydrocarbon group,wherein each hydrocarbon group optionally includes one or moreheteroatoms (e.g., oxygen, nitrogen, sulfur, silicon, or phosphorous);an aromatic group; a heteroaromatic group; and a heterocyclic group; orany combination thereof; wherein said groups, at each occurrence, areindependently unsubstituted or substituted with one or more suitablesubstituents; and

p and q, at each occurrence, are each independently an integer selectedfrom 1 to 200, preferably 1 to 20.

In certain embodiments, the foam compositions have formula (II-a),

wherein A and B are as defined above.

In certain embodiments, the foam compositions have formula (II-b),

In another aspect, disclosed are foam compositions comprising thereaction product of a compound of formula (a) with a compound of formula(b); or the reaction product of a compound of formula (a) with acompound of formula (c);

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms (e.g., oxygen, nitrogen, sulfur, silicon, orphosphorous); an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents; m is 2 to 200, preferably 2 to 20; and nis 2 to 200, preferably 2 to 20.

In certain embodiments, R¹ is a C₁-C₂₀ hydrocarbon group, wherein m is 2to 20. In certain embodiments, R¹ is a C₁-C₁₀ hydrocarbon group, whereinm is 2 to 10. In certain embodiments, R¹ is a C₁-C₅ hydrocarbon group,wherein m is 2 to 5. In certain embodiments, R¹ is a C₆ hydrocarbongroup and m is 3 or 4. In certain embodiments, R¹ is a C₄ hydrocarbongroup and m is 2, 3, or 4. In certain embodiments, R¹ is a C₃hydrocarbon group and m is 3, wherein the compound of formula (a) is

In certain embodiments, R¹ is a tetrahydrofuranyl or tetrahydropyranylgroup, wherein said groups are substituted or unsubstituted with one ormore suitable substituents. In certain embodiments, R¹ is atetrahydrofuranyl or tetrahydropyranyl group, wherein said groups aresubstituted or unsubstituted with one or more suitable substituents; andm is 4 to 7.

In certain embodiments, R¹ is derived from derived from compounds withtwo or more hydroxyl groups. Suitable multi-functional hydroxy compoundsinclude, for example, diols, triols, and other polyhydric alcohols. Incertain embodiments, R¹ is a polymer backbone. For example, R¹ may bederived from a polyalkylene glycol (e.g., polyethylene glycol,polypropylene glycol), a polysaccharide (e.g., cellulose, starch,amylose, amylopectin, tapioca, dextrin), or a polyvinyl alcohol.

In certain embodiments, the compound of formula (a) is amulti-functional acetoacetate ester compound. Exemplary compounds offormula (a) include, but are not limited to, alkyl diol diacetoacetates(also known as alkyl diol bisacetoacetates) such as, for example, butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentylglycoldiacetoacetate, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decanediacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, ethylene glycoldiacetoacetate, propylene glycol diacetoacetate; cyclohexanedimethanoldiacetoacetate; other diol diacetoacetates; alkyl triol triacetoacetates(also known as alkyl triol trisacetoacetates), such as, for example,trimethylol propane triacetoacetate, pentaerythritol triacetoacetate,glycerol triacetoacetate, or trimethylolethane triacetoacetate; and thelike. Further examples of suitable multi-functional acetoacetate estercompounds of formula (a) include tetra-, penta-, and higheracetoacetates of polyhydric alcohols (i.e., polyhydric alcohols on whichfour, five, or more hydroxyl groups are linked to acetoacetate groupsthrough ester linkages), including, for example, pentaerythritoltetraacetoacetate, dipentaerythritol pentaacetoacetate, anddipentaerythritol hexaacetoacetate. Further examples of suitablemulti-functional acetoacetate ester compounds of formula (a) includeethylene glycol bisacetoacetate, 1,2-propanediol bisacetoacetate,1,3-propanediol bisacetoacetate, 1,4-butanediol bisacetoacetate,neopentyl glycol bisacetoacetate, isosorbide bisacetoacetate,trimethylol propane tris acetoacetate, glycerol tris acetoacetate,castor oil tris acetoacetate, glucose acetoacetates (e.g., glucose trisacetoacetate, and glucose tetra acetoacetate), sucrose acetoacetates,sorbitol acetoacetates (e.g., sorbitol tris acetoacetate, and sorbitoltetra acetoacetate), and erythritol acetoacetates.

In certain embodiments, the compound of formula (a) is amulti-functional acetoacetate ester of a monosaccharide, a disaccharide,an oligosaccharide, a polysaccharide, or a combination thereof. Incertain embodiments, the compound of formula (a) is derived fromglucose, fructose, galactose, sucrose, lactulose, lactose, maltose,trehalose, celloboise, kojibiose, nigerose, isomaltose, β,β-trehalose,α,β-trehalose, sophorose, laminaribiose, gentiobiose, turanose,maltulose, palatinose, gentiobiulose, mannobiose, melibiose,melibiulose, rutinose, rutinulose, xylobiose, fructo-oligosaccharides,galactooligosaccharides, mannan oligosaccharides, arabinoxylans,cellulose, chitin, pectins, or a combination thereof. In certainembodiments, the compound of formula (a) is derived from sucrose. Incertain embodiments, the compound of formula (a) is derived fromsorbitol. In certain embodiments, the compound of formula (a) is derivedfrom erythritol.

In certain embodiments, the compound (a) has formula:

or a combination thereof; wherein R⁴, at each occurrence, isindependently selected from —H and —C(O)CH₂C(O)CH₃, provided that atleast two R⁴ groups are —C(O)CH₂C(O)CH₃; and R⁵ is —H or—C(O)CH₂C(O)CH₃.

In certain embodiments, R² is a C₁-C₂₀ hydrocarbon group, wherein n is 2to 20. In certain embodiments, R² is a saturated, linear or branchedC₁-C₂₀ hydrocarbon group, wherein n is 2 to 20. In certain embodiments,R² is a saturated, linear or branched C₂-C₁₀ hydrocarbon group, whereinn is 2 to 10. In certain embodiments, R² is a C₆ hydrocarbon group and nis 2, wherein the compound of formula (b) is

In certain embodiments, R² is aromatic-containing group. In certainembodiments, R² is an arylalkyl, and more specifically, an aryldialkylgroup. In certain embodiments, R² is an aryldialkyl group and n is 2,wherein the compound of formula (b) is

In certain embodiments, the compound of formula (b) is amulti-functional amine compound. In certain embodiments, the compound offormula (b) is an alkylene diamine, an alkylene triamine, an alkylenetetraamine, or the like. In certain embodiments, the compound of formula(b) is an aromatic-containing multi-functional amine. Suitablemulti-functional amine compounds include, for example, ethylene diamine,hexamethylene diamine, 2-methyl-1,5-diaminopentane, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, meta-phenylenediamine,para-phenylenediamine, meta-xylenediamine, and diaminodiphenyl sulfone.

In certain embodiments, the compound of formula (b) has formula:

or a combination thereof

In certain embodiments, R³ is a C₂-C₂₀-alkylenyl, or a C₂-C₁₀-alkylenyl.In certain embodiments, R³ is a C₆-alkylenyl wherein the compound offormula (c) is

Compounds and compositions disclosed herein may contain asymmetriccenters and can thus occur as racemates and racemic mixtures, singleenantiomers, diastereomeric mixtures and individual diastereomers.Additional asymmetric centers may be present depending upon the natureof the various substituents on the molecule. Each such asymmetric centerwill independently produce two optical isomers and it is intended thatall of the possible optical isomers and diastereomers in mixtures and aspure or partially purified compounds are included within the scope ofthis invention. The present invention is meant to comprehend all suchisomeric forms of these compounds.

3. SYNTHETIC METHODS

The disclosed compositions can be better understood in connection withthe following synthetic schemes and methods which illustrate a means bywhich the compositions can be prepared.

Acetoacetylated compounds of formula (a) can be prepared as shown inScheme 1. A polyhydric alcohol compound of formula (1) can be treatedwith tert-butyl acetoacetate of formula (2) to provide amulti-functional acetoacetate ester compound of formula (a).

Glycerol triacetoacetate and sucrose multi-functionalized withtriacetoacetate groups were each synthesized according to Scheme 1. Theweight of evolved tert-butanol showed about 84% (6.7-7.0) of theavailable hydroxyl groups of sucrose had reacted (8.0 are available).Infrared (IR) analysis showed typical ketoester absorbances at 1750 cm⁻¹and 1720 cm⁻¹ for the carbonyls, and 1630 cm⁻¹ for the enol. The datafor glycerol triacetoacetate showed about 100% reaction (2.9-3.0) of thehydroxyl groups; and the IR analysis showed similar ketoesterabsorbances for the diagnostic region.

Foam compositions of formula (I-b), for example, can be synthesized asshown in Scheme 2. Glycerol triacetoacetate and xylene diamine can becombined to provide a foam composition of formula (I-b). The waterproduced in the reaction may serve as a blowing agent (e.g., a chemicalblowing agent) to aid in the foam production.

Foam compositions of formula (II-b), for example, can be synthesized asshown in Scheme 3. Glycerol triacetoacetate and hexane diacrylate can becombined in the presence of a base (e.g.,1,8-diazabicyclo[5.4.0]undec-7-ene) to provide a foam composition offormula (II-b).

In certain embodiments, the products may be further modified, forexample, by manipulation of substituents. These manipulations mayinclude, but are not limited to, reduction, oxidation, organometalliccross-coupling, alkylation, acylation, and hydrolysis reactions whichare commonly known to those skilled in the art. In some cases, the orderof carrying out the foregoing reaction schemes may be varied tofacilitate the reaction or to avoid unwanted reaction products.

In certain embodiments, one or more catalysts may be used in theforegoing reactions to initiate or assist with foam formation. Suitablemetal-based catalysts include, but are not limited to, catalystscomprising tin, bismuth, zinc, iron, manganese, nickel, or cobalt, or acombination thereof. For example, a tin catalyst (e.g.,dimethylbis[(1-oxoneodecyl)oxy]stannane) may be used in the reaction ofScheme 1. In certain embodiments, the reactions may further includesolvents or additives. For example, one or more blowing agents orsurfactants may be present to aid in the formation of the physical foamstructure or augment foam physical properties.

4. ADDITIVES

The foam compositions can include one or more additives.

The foam compositions can include one or more blowing agents. Suitableblowing agents include compounds with low boiling points which arevaporized during the exothermic polymerization reaction. Such blowingagents are generally inert and therefore do not decompose or reactduring the polymerization reaction. In certain embodiments, at least oneof the one or more blowing agents has a gas phase thermal conductivityof less than or equal to 0.016 W/m·K or less than or equal to 0.014W/m·K or less than or equal to 0.012 W/m·K at 25° C. Examples of inertblowing agents include, but are not limited to, carbon dioxide,chlorofluorocarbons, hydrogenated fluorocarbons, hydrogenatedchlorofluorocarbons, acetone, and low-boiling hydrocarbons such ascyclopentane, isopentane, n-pentane, and their mixtures. Specificexemplary blowing agents include, but are not limited to,1,1,4,4,4-hexafluoro-2-butene; carbon dioxide; hydrocarbons such aspentane, isopentane, cyclopentane petroleum ether, and ether;hydrochlorofluorocarbons such as 1,1-dichloro-1-fluoroethane(HCFC-141b); 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123);1-chloro-1,1-difluoroethane (HCFC-142b); 1,1,1,2-tetrafluoroethane(HCFC-134a); 1,1,1,3,3-pentafluoropropane (HFC-245fa) available fromHoneywell (Morristown, N.J.); 1,1,1,3,3-pentafluorobutane (HFC-365)available as Solkane® 365mfc from Solvay Chemicals (Bruxelles, Belgium);incompletely halogenated hydrocarbons such as 2-chloropropane;fluorocarbons such as dichlorodifluoromethane,1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114),trichlorotrifluoroethane (CFC-113), trichloromonofluoromethane (CFC-11),z 1,1,1,4,4,4-hexafluoro-2-butene (under the trade names FEA 1100 andFormacel® 1100, supplied by DuPont; the CAS (Chemical Abstracts System)Number is 692-49-9). In certain embodiments, the blowing agent is water.

In certain embodiments, a blowing agent is generated in situ during foamformation. For example, enamine formation upon reaction of acetoacetateesters with amines yields water as a byproduct, and the water may act asa blowing agent (e.g., a chemical blowing agent).

The foam compositions can include one or more surfactants. A surfactantcan be employed to stabilize the foaming reaction mixture while curing.Such surfactants normally comprise a liquid or solid organosiliconecompound. The surfactants are employed in amounts sufficient tostabilize the foaming reaction mixture against collapse and to preventthe formation of large, uneven cells. Suitable surfactants include, butare not limited to, those sold under the trade name “TEGOSTAB®” byGoldschmidt Chemical Company, such as TEGOSTAB® B-8407 surfactant;TEGOSTAB® B-8474 surfactant; TEGOSTAB® B-2219 surfactant; TEGOSTAB®B-8870 surfactant; TEGOSTAB® B-8433 surfactant; TEGOSTAB® B-8404surfactant; TEGOSTAB® B-8462 surfactant; TEGOSTAB® B-8467 surfactant;TEGOSTAB® B-8465 surfactant; and TEGOSTAB® B-8470 surfactant. Anotherexample of a suitable surfactant is SURFONIC® N-120 surfactant which iscommercially available from Huntsman Petrochemical Corporation of TheWoodlands, Tex. Surfactants may also include silicone surfactants andcombinations of surfactants. In certain embodiments, about 0.1% to about5% by weight of surfactant based on the total weight of all foamingingredients are used. In certain embodiments, about 1.5% to about 3% byweight of surfactant based on the total weight of all foamingingredients are used.

The foam compositions can include one or more flame retardants. Suitableflame retardants include, but are not limited to, phosphorus-containingflame retardants selected from the groups of the mono- and oligomericphosphoric and phosphonic esters, phosphonate amines, phosphonates,phosphinates, metal dialkylphosphinates (e.g., aluminiumtris[dialkylphosphinates] and zinc bis[dialkylphosphinates]),phosphites, hypophosphites, phosphine oxides, phosphazenes; andnitrogen-containing flame retardants individually or in a mixture, suchas for example, melamine oxalate, melamine phosphate prim., melaminephosphate sec., and melamine pyrophosphate sec., reaction products ofmelamine with condensed phosphoric acids and reaction products ofcondensates of melamine with phosphoric acid or with condensedphosphoric acids, in particular melamine polyphosphate, and also thereaction products of melamine and polyphosphoric acid with basicaluminium compounds, with basic magnesium compounds and/or with basiczinc compounds, and also melamine cyanurate and amine neopentyl glycolborate; guanidine salts, such as guanidine carbonate, guanidinecyanurate prim., guanidine phosphate prim., guanidine phosphate sec.,guanidine sulphate prim., guanidine sulphate sec., guanidinepentaerythrityl borate, guanidine neopentyl glycol borate, ureaphosphate, and urea cyanurate. It is also possible to use condensates ofmelamine, in particular melem, melam, melon, or compounds of this typewith higher level of condensation, and reaction products of these withcondensed phosphoric acids; tris(hydroxyethyl) isocyanurate and reactionproducts thereof with carboxylic acids, benzoguanamine and its adductsand its salts, and its products substituted on nitrogen, and alsoadducts and salts of these. Other nitrogen-containing components thatcan be used are allantoin compounds, and salts of these with phosphoricacid, boric acid or pyrophosphoric acid, and also glycol urils and saltsof these; and any combination of the foregoing. In certain embodiments,the flame retardant is selected from phosphate flame retardants,melamine flame retardants, tris(2-chloropropyl)phosphate (TCPP),tris(2-chloroethyl)phosphate (TCEP),tris(1,3-dichloroisopropyl)phosphate (TDCPP), dimethylmethylphosphonate(DMMP), and diethylene glycol (DEG) and propylene glycol (PG) esters oftetrabromophthalic anhydride (ME-TBPA), or any combination thereof. Incertain embodiments, the disclosed compositions can include expandedgraphite as a flame retardant. When crystalline flaky graphite isoxidized with concentrated sulfuric acid and a hydrogen peroxidesolution, washed with water, and then put into a high-temperatureexpansion furnace, it is expanded in the direction of a c axis ofgraphite crystal. The crystalline flaky graphite expanded to 100˜700% ofinitial volume thereof is referred to as “expanded graphite.”

The foam compositions can include one or more catalysts. Suitablecatalysts include, but are not limited to, tin catalysts (e.g.,dimethylbis[(1-oxoneodecyl)oxy]stannane)).

A variety of other ingredients may be included in the formulations formaking foams. Examples of optional components include, but are notlimited to, cell stabilizers such as silicones, crosslinking agents,chain extenders, pigments, preservatives, antioxidants, reinforcingagents, antistatic agents, fillers and combinations of any of these.

5. FOAM PROPERTIES

The disclosed foam compositions can have one or more advantageousproperties.

The foam compositions may have advantageous thermal insulationproperties, assessed by thermal conductivity and thermal resistance.Thermal conductivity is an intrinsic property of a material thatmeasures its capacity to sustain heat flow. The symbol used to denotethermal conductivity is k (or lambda, λ), referred to as the material'sK-value. The reciprocal of thermal conductivity is thermal resistivity,an intrinsic property of a material to resist one-dimensional heat flow,referred to as the material's R-value. Thermal conductivity can bemeasured according to ASTM-0518.

The effectiveness of thermal insulation can be measured by its thermalresistance. In the insulation industry, the standard measure of aninsulator's ability to resist thermal energy transfer is referred to asthe insulation's R-value. The higher the R-value, the more effective theinsulation. Knowing a material's R-value allows contractors, buildinginspectors, and homeowners to compare products and calculate the amountof insulation needed for a particular construction project.Additionally, regulatory agencies use R-values to establish recommendedor mandatory guidelines for new buildings.

The disclosed compositions may have a K value of 0.125 to 0.3 BTU perinch/° F.-ft²-h. The foam compositions may have a K value of 0.35 BTUper inch/° F.-ft²-h or less, 0.25 BTU per inch/° F.-ft²-h or less, 0.2BTU per inch/° F.-ft²-h or less, 0.17 BTU per inch/° F.-ft²-h or less,0.14 BTU per inch/° F.-ft²-h or less, or 0.13 BTU per inch/° F.-ft²-h orless.

The disclosed foam compositions may have an R value of 3.5 to 8°F.-ft²-h/BTU per inch. The foam compositions may have an R value of 3°F.-ft²-h/BTU per inch or greater, 4° F.-ft²-h/BTU per inch or greater,5° F.-ft²-h/BTU per inch or greater, 6° F.-ft²-h/BTU per inch orgreater, 7° F.-ft²-h/BTU per inch or greater, or 8° F.-ft²-h/BTU perinch or greater.

The foam compositions may have a glass transition temperature of 40° C.to 150° C.

The foam compositions may have a foam density of 0.1 lb/ft³ to 30lb/ft³, 0.5 lb/ft³ to 10 lb/ft³, 1.5 lb/ft³ to 10 lb/ft³, 1.7 lb/ft³ to3.5 lb/ft³, 1.5 lb/ft³ to 2.5 lb/ft³, or 1.7 lb/ft³ to 2.5 lb/ft³.

The foam compositions may have a cream time of 1 second to 5 seconds, or2 seconds to 4 seconds. The foam compositions may have a start to risetime of 2 seconds to 17 seconds, or 4 seconds to 8 seconds. The foamcompositions may have a tack free time of 4 seconds to 30 seconds, or 8seconds to 12 seconds.

The foam compositions may be resistant to molding or fungus growth, asmeasured by ASTM C1338. The foam compositions may not serve as a foodsource for insects or rodents.

The foam compositions may have negligible air infiltration, as measuredaccording to ASTM E283-04. The foam compositions may have a water vaporinfiltration of greater than 1 perm or 5.72×10⁻⁸ g/Pa-s-m².

The foam compositions may have little or no odor.

6. METHODS OF USE

The disclosed foam compositions are useful in a variety of sealing andinsulation applications. These include, for example, building insulationsuch as for walls, foundations, floors and roofs; gap and crack fillingand crack repair applications in buildings, masonry and otherstructures; vehicular cavity-filling applications, and the like. Thefoams are also useful in producing boardstock insulation and/orconstruction materials by spraying or applying the uncured foam onto afacing material (such as, for example, a fiber layer, a wood or metallayer, and the like). The foam compositions may be injected for use inlow temperature applications (e.g., refrigerators, freezers,refrigerated trailers, walk-in cold-storage).

The foam compositions can be applied using spray foam equipment. Thespray foam equipment may include separate containers for each of theA-side and B-side components. The containers can each be in fluidconnection with a separate conduit, which each are in fluidcommunication with a mixing chamber which in turn is in fluidcommunication with a nozzle. Upon opening the containers (via theopening of a suitable valve in each of the containers), the A-sidecomponent and B-side component can be pneumatically pumped from theircontainers into the respective conduits. The A-side and B-sidecomponents may then be brought to the mixing chamber under pressure froman electric or hydraulic pump, for example at a pressure of 500-2,000psi, 800-2,000 psi, or 900-1,200 psi, and combined in a mixing device toform a reaction mixture. The mixing device may be a static mixer, a mixchamber, or other mixhead. The reaction mixture can then be expelledthrough a nozzle or other orifice. The conduit before the spray gun canbe heated, for example, to a temperature of 70° F. to 200° F. or from90° F. to 140° F. The expelled reaction mixture typically forms a spraywhich is directed to a mold or other surface upon which the polymericfoam is to be applied. The expelled reaction mixture typically forms aspray or a foam bead, depending in part on the nozzle size and type andthe viscosity of the exiting material, which is directed to a mold orother surface upon which the polymeric foam is to be applied. Thereaction mixture is then cured in situ. Suitable spray foam equipmentincludes that described in, for example, U.S. Pat. No. 8,568,104, U.S.Pat. No. 6,991,185, and U.S. Published Patent Application No.2004-0109992, each of which is herein fully incorporated by reference inits entirety. An exemplary electric pump and proportioner that may beused includes an electric foam proportioner for medium- to high-outputfoam insulation applications that applies up to 30 lb (13.6 kg) perminute (e.g., Reactor E-20 available from Graco, Minneapolis, Minn.). Anexemplary hydraulic pump and proportioner that may be used includes ahydraulic foam proportioner for medium to high-output foam applicationsand roofing projects that applies up to 52 lb (23.6 kg) per minute(e.g., Reactor H-25, H-40 or H-50 available from Graco). An exemplaryair purge spray gun may be a plural-component spray gun for high outputspray foam applications, available from Graco.

In certain embodiments, a preblend of certain materials is preparedprior to reacting the foam components [e.g., the compound of formula (a)and the compound of formula (b)]. For example, foam expansion agents,surfactants, catalysts and other foaming ingredients can eachindividually be blended with one or both of the foam reactants toprovide one or more blends of the reaction components; and then therespective blend(s) can be combined to provide the reaction mixtureresulting in a foam composition. Alternatively, all the foamingingredients may be introduced individually to the mixing zone where thefoam reactants [e.g., the compound of formula (a) and the compound offormula (b)] are contacted. It is also possible to pre-react all or aportion of the foam reactants to form a prepolymer (e.g., a polymer withreduced crosslinking).

7. KITS

Disclosed are kits for conveniently and effectively implementing thedisclosed methods. Such kits may include a compound or composition ofthe invention, and optionally one or more of instructions, packaging,and dispensers. Kit components may be packaged for either manual orpartially or wholly automated practice of the foregoing methods. Inother certain embodiments, a kit includes the disclosed foam reactants,and optionally instructions for their application as a foam material.

The disclosed compounds, compositions, methods and processes will bebetter understood by reference to the following examples, which areintended as an illustration of and not a limitation upon the scope ofthe invention.

8. EXAMPLES

Differential scanning calorimetry (DSC) was used to determine glasstransition temperature. Thermogravimetric analysis was used to determinedecomposition onset temperature. Equipment that can be used to preparefoam compositions includes a high speed mixer; a stop watch; a balance;and calipers, among other equipment.

A. Synthesis of Acetoacetate Ester Starting Materials Example 1Synthesis of Sucrose and Glycerin Acetoacetates Using Tert-ButylAcetoacetate

Acetoacetylation was conducted at two ratios of sucrose to glycerin: 4/1and 5/1. For the 4/1 preparation, 160 grams of sucrose was charged to a2 L flask equipped with a mechanical stirrer, Dean-Stark trap, refluxcondenser and temperature sensing thermocouple attached to aThermowatch. Forty grams of glycerin was added and this mixture washeated at 100° C. until a quasi-homogeneous mixture was obtained(1.0-1.5 hours, some of the sucrose was dissolved, but it was all atleast coated with glycerin). Tert-butyl acetoacetate (864 grams) wasadded and this mixture was heated at 125-135° C. until the evolution oft-butanol ceased (3.0-3.5 hours). Samples were taken for viscositymeasurements. Before any t-butanol had evolved the viscosity was about2,600-3,000 centipoise (cps). As the reaction proceeded the viscositydecreased at first (down to about 200 cps), however, at the end theviscosity was up to 3,300 cps.

For the 5/1 preparation, the same procedure was used with theappropriate ratios of sucrose and glycerin (167 grams sucrose and 33grams of glycerin).

Example 2 Synthesis of Sucrose and Glycerin Acetoacetates Using2,6-trimethyl-4H-1,3-dioxan-4-one

Sucrose and glycerin acetoacetates were prepared using2,2,6-trimethyl-4H-1,3-dioxan-4-one (structure below) as a startingmaterial. A 2 L flask equipped with a Dean-Stark trap, reflux condenserand thermometer, was charged with 100.3 g of sucrose and 335 g of2,2,6-trimethyl-4H-1,3-dioxan-4-one (TDO). The reaction mixture wasbrought to 96° C. at which point the evolution of acetone commenced.Acetone was collected over the next 1.5 hours until distillationstopped. The quantity of acetone collected showed that ˜98 mol % of theavailable hydroxyl groups had reacted. The product was then tested asper the material obtained from the t-butyl acetoacetate synthesis. Itper formed the same according to the previous Examples. This syntheticroute provides for synthesis of the product at lower temperature and athigher conversion levels.

B. Preparation of Foam Compositions

Table 1 summarizes exemplary components used to prepare the foamcompositions. The components are prepared by methods described herein ormethods known in the art. All other chemical components are purchasedfrom commercial sources.

TABLE 1 Sucrose Acetoacetate Glycerine Acetoacetate Tin Catalyst(dimethylbis[(1-oxoneodecyl)oxy] stannane) Meta xylene diamine (MXDA)Dytek A (2-methyl-1,5-diaminopentane) Tegostab B-8407 (polyethermodified siloxane surfactant) Tegostab B-8221 (surfactant)Tris(2-chloropropyl)phosphate (TCPP)-fire retardant HFC-365 mfg (blowingagent)

Example 3

Foam compositions were prepared using a two-part system (e.g., side Aand side B). Table 2 summarizes the components and amounts used toprepare an exemplary foam composition.

TABLE 2 Side A Sucrose Acetoacetate 25.00 grams (gr) GlycerineAcetoacetate 25.00 gr Tin Catalyst (dimethylbis[(1-oxoneodecyl)oxy]stannane) 1.49 gr Side B Meta xylene diamine (MXDA) 14.83 gr Dytek A(2-methyl-1,5-diaminopentane) 9.83 gr Tegostab B-8407 (polyethermodified siloxane surfactant) 0.80 gr Tegostab B-8221 (surfactant) 0.50gr Tris(2-chloropropyl)phosphate (TCPP)-fire retardant 15.38 gr HFC-365mfg (blowing agent) 3.00 gr

Side A: 50 grams of a 1:1 mixture (by weight) of sucrose acetoacetateand glycerine acetoacetate were measured into a container (Side A). 1.49grams of catalyst were added to side A. Side A was mixed and set to theside. Hexane diol diacrylate (0.40 gr) was optionally added to side A.

Side B: 14.83 grams of MXDA were added to a new container (Side B). 9.83grams of Dytek A was added to side B. 0.80 grams of Tegostab B-8407 wasadded to side B. 0.50 grams of Tegostab B-8221 was added to side B.15.38 grams of Tris(2-chloropropyl)phosphate (TCPP) was added to side B.3.00 grams of blowing agent was added side B. Side B was mixed until aclear solution was obtained.

A rigid foam was prepared by adding Side B to Side A. The mixture wasstirred under high shear for 3-5 seconds. A foam bun resulted. A creamtime of 2-3 seconds was observed. The start to rise time of the foam was5-14 seconds depending on catalyst composition and catalystconcentration. Tack-free time occurred at 5-8 seconds as well. Themeasured density of the foam was 2.7 to 5 lbs/ft³. The measured T_(g) ofthe foam was 57° C. The decomposition onset temperature of the foam was210° C.

The formulation of Table 2 generated a foam with good cell structure,which is small and symmetric throughout the foam.

Example 4

Foam compositions can be prepared with acetoacetates mixed with diaminesand a surfactant. Table 3 summarizes the components and amounts used toprepare an exemplary foam composition.

TABLE 3 Side A Sucrose Acetoacetate 25.00 grams (gr) GlycerineAcetoacetate 25.00 gr Side B Meta xylene diamine (MXDA) 14.83 gr Dytek A(2-methyl-1,5-diaminopentane) 9.83 gr Tegostab B-8407 (polyethermodified siloxane surfactant) 0.80 gr

The formulation of Table 3 provided a foam with a cream time of about3-5 seconds. The start to rise time of the foam was 13-18 seconds. Thedensity of the foam was determined to be about 5 lbs/ft³. The foam wasprepared without the use of a physical blowing agent.

Prophetic Example 1

Bulk up the composition in Example 3 to 15,000 total grams for each sidein 5 gallon plastic pails. The compositions are fed via pneumatictransfer pumps to a Graco HVR proportioner. The proportioner settingsare as follows: Material Temperature 75 F, A and B side preheaters andline temperatures range from 90 F to 120 F and the pump pressure rangefrom 1000 to 1200 psi. The resulting foam ranges in density from 1.7lb/cubic ft to 2.7 lb/cubic ft and exhibits normal cell structure andphysical foam characteristics.

Prophetic Example 2

Bulk up the composition in Example 3 to 15,000 total grams for each sidein 5 gallon plastic pails. The compositions are fed via pneumatictransfer pumps to a Graco E20 proportioner. The proportioner settingsare as follows: Material Temperature 75 F, A and B side preheaters andline temperatures range from 110 F to 160 F and the pump pressure rangesfrom 800 to 1000 psi. The resulting foam ranges in density from 1.3lb/cubic ft to 1.8 lb/cubic ft and exhibits normal cell structure andphysical foam characteristics.

It is understood that the foregoing detailed description andaccompanying examples are merely illustrative and are not to be taken aslimitations upon the scope of the invention, which is defined solely bythe appended claims and their equivalents.

For reasons of completeness, various aspects of the disclosure are setout in the following numbered clauses:

Clause 1. A foam comprising the reaction product of a compound offormula (a) with a compound of formula (b); or the reaction product of acompound of formula (a) with a compound of formula (c);

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms; an aromatic group; a heteroaromatic group; anda heterocyclic group; or any combination thereof; wherein said groups,at each occurrence, are independently unsubstituted or substituted withone or more suitable substituents; m is 2 to 200; and n is 2 to 200.

Clause 2. The foam of clause 1, wherein m=3.

Clause 3. The foam of clause 1 or clause 2, wherein the compound offormula (a) is

Clause 4. The foam of clause 1, wherein m=7 or 8.

Clause 5. The foam of clause 1 or clause 4, wherein the compound offormula (a) is

wherein R⁴, at each occurrence, is independently selected from —H and—C(O)CH₂C(O)CH₃, provided that at least two R⁴ groups are—C(O)CH₂C(O)CH₃; and R⁵ is —H or —C(O)CH₂C(O)CH₃.

Clause 6. The foam of any one of clauses 1-5, wherein n=2.

Clause 7. The foam of any one of clauses 1-6, wherein the compound offormula (b) is

or a combination thereof

Clause 8. The foam of any one of clauses 1-7, wherein R³ isC₂-C₁₀-alkylenyl.

Clause 9. The foam of any one of clauses 1-8, wherein the compound offormula (c) is

Clause 10. The foam of any one of clauses 1-9, wherein the foam hasformula (I-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.

Clause 11. The foam of clause 10, wherein A is derived from glyceroltriacetoacetate, a sorbitol acetoacetate, an erythritol acetoacetate, amulti-functionalized acetoacetate ester of a monosaccharide or adisaccharide, or a combination thereof; and B is derived from xylenediamine, 2-methyl-1,5-diaminopentane, or a combination thereof.

Clause 12. The foam of clause 11, wherein the disaccharide is sucrose.

Clause 13. The foam of clause 1, wherein the foam has formula (I-b),

Clause 14. The foam of any one of clauses 1-9, wherein the foam hasformula (II-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.

Clause 15. The foam of clause 1, wherein the foam has formula (II-b),

Clause 16. The foam of any one of clauses 1-13, wherein water producedas a consequence of reaction between compound (a) and compound (b) actsas a chemical blowing agent.

Clause 17. The foam of any one of clauses 1-16, wherein the foam is arigid foam or a semi-rigid foam.

Clause 18. A method of preparing a foam, comprising reacting a compoundof formula (a) with a compound of formula (b); or reacting a compound offormula (a) with a compound of formula (c):

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms; an aromatic group; a heteroaromatic group; anda heterocyclic group; or any combination thereof; wherein said groups,at each occurrence, are independently unsubstituted or substituted withone or more suitable substituents; m is 2 to 200; and n is 2 to 200.

Clause 19. The method of clause 18, wherein m=3.

Clause 20. The method of clause 18 or clause 19, wherein the compound offormula (a) is

Clause 21. The method of clause 18, wherein m=7 or 8.

Clause 22. The method of clause 18 or clause 21, wherein the compound offormula (a) is

wherein R⁴, at each occurrence, is independently selected from —H and—C(O)CH₂C(O)CH₃, provided that at least two R⁴ groups are—C(O)CH₂C(O)CH₃; and R⁵ is —H or —C(O)CH₂C(O)CH₃.

Clause 23. The method of any one of clauses 18-22, wherein n=2.

Clause 24. The method of any one of clauses 18-23, wherein the compoundof formula (b) is

or a combination thereof.

Clause 25. The method of any one of clauses 18-24, wherein R³ isC₂-C₁₀-alkylenyl.

Clause 26. The method of any one of clauses 18-25, wherein the compoundof formula (c) is

Clause 27. The method of any one of clauses 18-26, wherein the foam hasformula (I-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.

Clause 28. The method of clause 27, wherein A is derived from glyceroltriacetoacetate, a sorbitol acetoacetate, an erythritol acetoacetate, amulti-functionalized acetoacetate ester of a monosaccharide or adisaccharide, or a combination thereof; and B is derived from xylenediamine, 2-methyl-1,5-diaminopentane, or a combination thereof.

Clause 29. The method of clause 28, wherein the disaccharide is sucrose.

Clause 30. The method of clause 18, wherein the foam has formula (I-b),

Clause 31. The method of any one of clauses 18-26, wherein the foam hasformula (II-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.

Clause 32. The method of clause 18, wherein the foam has formula (II-b),

Clause 33. The method of any one of clauses 18-30, wherein waterproduced as a consequence of reaction between compound (a) and compound(b) acts as a chemical blowing agent.

Clause 34. The method of any one of clauses 18-33, wherein the foam is arigid foam or a semi-rigid foam.

Clause 35. The method of any one of clauses 18-34, wherein the compoundof formula (a) and the compound of formula (b); or the compound offormula (a) and the compound of formula (c) are pneumatically pumpedfrom separate first and second containers to respective first and secondconduits.

Clause 36. The method of clause 35, wherein the compound of formula (a)and the compound of formula (b); or the compound of formula (a) and thecompound of formula (c) are brought from their respective first andsecond conduits to a mixing chamber under pressure from an electric orhydraulic pump, the compound of formula (a) and the compound of formula(b); or the compound of formula (a) and the compound of formula (c)forming a reaction mixture.

Clause 37. The method of clause 36, wherein the pressure is 500-2,000psi, 800-2,000 psi, or 900-1,200 psi.

Clause 38. The method of clause 36 or clause 37, wherein the reactionmixture is pumped from the mixing chamber to a third conduit, and fromthe third conduit to a nozzle or orifice, wherein the reaction mixtureis expelled through the nozzle or orifice.

Clause 39. The method of clause 38, wherein the third conduit is heatedto a temperature of 70° F. to 200° F. or from 90° F. to 140° F.

Clause 40. The method of clause 38 or clause 39, wherein the expelledreaction mixture is directed to a mold or other surface.

Various changes and modifications to the disclosed embodiments will beapparent to those skilled in the art. Such changes and modifications,including without limitation those relating to the chemical structures,substituents, derivatives, intermediates, syntheses, compositions,formulations, or methods of use of the invention, may be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A foam comprising the reaction product of acompound of formula (a) with a compound of formula (b); or the reactionproduct of a compound of formula (a) with a compound of formula (c);

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms; an aromatic group; a heteroaromatic group; anda heterocyclic group; or any combination thereof; wherein said groups,at each occurrence, are independently unsubstituted or substituted withone or more suitable substituents; m is 2 to 200; and n is 2 to
 200. 2.The foam of claim 1, wherein m=3.
 3. The foam of claim 2, wherein thecompound of formula (a) is


4. The foam of claim 1, wherein m=7 or
 8. 5. The foam of claim 4,wherein the compound of formula (a) is

wherein R⁴, at each occurrence, is independently selected from —H and—C(O)CH₂C(O)CH₃, provided that at least two R⁴ groups are—C(O)CH₂C(O)CH₃; and R⁵ is —H or —C(O)CH₂C(O)CH₃.
 6. The foam of claim1, wherein n=2.
 7. The foam of claim 6, wherein the compound of formula(b) is

or a combination thereof.
 8. The foam of claim 1, wherein R³ isC₂-C₁₀-alkylenyl.
 9. The foam of claim 8, wherein the compound offormula (c) is


10. The foam of claim 1, wherein the foam has formula (I-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.
 11. The foam of claim 10, wherein A isderived from glycerol triacetoacetate, a sorbitol acetoacetate, anerythritol acetoacetate, a multi-functionalized acetoacetate ester of amonosaccharide or a disaccharide, or a combination thereof; and B isderived from xylene diamine, 2-methyl-1,5-diaminopentane, or acombination thereof.
 12. The foam of claim 11, wherein the disaccharideis sucrose.
 13. The foam of claim 1, wherein the foam has formula (I-b),


14. The foam of claim 1, wherein the foam has formula (II-a):

wherein A and B, at each occurrence, are each independently selectedfrom a saturated or unsaturated, linear, branched, or cyclic hydrocarbongroup, wherein each hydrocarbon group optionally includes one or moreheteroatoms; an aromatic group; a heteroaromatic group; and aheterocyclic group; or any combination thereof; wherein said groups, ateach occurrence, are independently unsubstituted or substituted with oneor more suitable substituents.
 15. The foam of claim 1, wherein the foamhas formula (II-b),


16. The foam of claim 1, wherein water produced as a consequence ofreaction between compound (a) and compound (b) acts as a chemicalblowing agent.
 17. The foam of claim 1, wherein the foam is a rigid foamor a semi-rigid foam.
 18. A method of preparing a foam, comprisingreacting a compound of formula (a) with a compound of formula (b); orreacting a compound of formula (a) with a compound of formula (c):

wherein R¹, R², and R³, at each occurrence, are each independentlyselected from a saturated or unsaturated, linear, branched, or cyclichydrocarbon group, wherein each hydrocarbon group optionally includesone or more heteroatoms; an aromatic group; a heteroaromatic group; anda heterocyclic group; or any combination thereof; wherein said groups,at each occurrence, are independently unsubstituted or substituted withone or more suitable substituents; m is 2 to 200; and n is 2 to
 200. 19.The method of claim 18, wherein the compound of formula (a) and thecompound of formula (b); or the compound of formula (a) and the compoundof formula (c) are pneumatically pumped from separate first and secondcontainers to respective first and second conduits.
 20. The method ofclaim 19, wherein the compound of formula (a) and the compound offormula (b); or the compound of formula (a) and the compound of formula(c) are brought from their respective first and second conduits to amixing chamber under pressure from an electric or hydraulic pump, thecompound of formula (a) and the compound of formula (b); or the compoundof formula (a) and the compound of formula (c) forming a reactionmixture.
 21. The method of claim 20, wherein the pressure is 500-2,000psi.
 22. The method of claim 20, wherein the reaction mixture is pumpedfrom the mixing chamber through a third conduit to a nozzle or orificeand expelled through the nozzle or orifice.
 23. The method of claim 22,wherein the third conduit is heated to a temperature of 70° F. to 200°F.
 24. The method of claim 22, wherein the expelled reaction mixture isdirected to a mold or other surface.